Process for treating fabrics



PatentedFeb. 1, 1944 V 2,340,358 raocassron resume .mnmcs Howard A. youn Westfield, n.1,, assignor to United States Rubber Company, New Yor N. Y., a corporation of New Jersey Serial No. 489,540

No Drawing; Application June 3. 1943,

12 Claims. '(CL 117-161) This invention relates to a process for treating fabrics, more particularly to a, process for treating fabrics with water-insoluble synthetic resins.

.Aqueous dispersions of water-insoluble syn-' thetic resins have been used to treat fabrics in various ways.- In some cases the fabrics are saturated'with'the resin emulsion or dispersion,

and the treated fabric dried to leave a resin deposit on the fabric. Such methods of depositing resins on the fabric impart a harsh and boardy feel to the material. 4 j

In my prior Patent 2,173,243 there=is'disclosed a process for gradually depositing particles of treating material, including artificial resins, on fabric by treatment withan aqueous-dispersion of the treating material which gradually exhausts the dispersed particles of resin or other material onto the fabric: as the fabric is permitted to remain in contact with the dispersion bath. When resin particles are deposited on a fabric by the process of this prior patent, the fabric retains to a great extent the feel and "handle of an untreated fabric.

The present invention is an improvement over the process of my prior Patent 2,173,243 in that larger particles ofwater insoluble synthetic resins are deposited from an aqueous medium onto the fabric, which in the case of knitted fabrics, such as stockings, more effectively locks together the filaments of the yarn thus inhibiting snaggin and adding durability to the hosiery.

According to the present invention, the fabric is associated with a dilute aqueous bath containing particles of water-insoluble synthetic resin which have been agglomerated from the dispersed state to the form of flocs which are clearly macroscopic and readily separable from the aqueous medium on standing. The water-insoluble resin or dispersion thereof may be compounded as by the addition of modifiers, fillers, vulcanizing or curing ingredients, and other resins. when the colloidal resin particles are agglomerated from the dispersed state to the flocculated state before deposition according to the present invention, the various compounding ingredients for the resin that may also be dispersed in the aqueous medium become agglomerated along with the resin particles into flocs which contain representative proportions of the various compounding ingredients. Hence, there is the additional advantage over the prior art depositions from a colloidal dispersion of a water-insoluble resin containing dispersed compounding ingredients that the flocs of resin as they are deposited onto the fabric from the agglomerated treating bath of the present. invention will inherently contain representative proportions of all the compounding ingredients inthe bath, as distinguished from the independent deposition of resin particles and particles of compounding ingredients from a deposition bath in which'the resin and compounding materials areindividually dispersed in colloidal condition, as in the priorart. Theaqueousdlsp rsion of the waterinsoluble synthetic resin may be prepared from the solid resin by dispersing the same, with the addition of plasticizers and dispersing agents if desired, in an aqueous medium by means of a colloid mill, .or by addinga plasticizer, if desired, and mixing in a hydrophilic colloidal dispersing agent and masticating with additions of water until the resin becomes dispersed in the aqueous medium, as is well knownin the art, or

the resin itself maybe prepared asbycondensation or polymerization in an aqueous medium. Various compounding ingredients may be added to the resin before dispersing, or to the dispersion after preparation. Various water-insoluble synthetic resins dispersed in an aqueous medium are available commercially. The waterinsoluble resin particles in any aqueous dispersion, once the resin particles are colloidally dispersed in an aqueous medium, may be agglomerated or flocculated from the dispersed condition by the addition of various agglomerating or flocculating agents-in the presence of a sufllcient amount of protective to prevent the dispersed resin particles from completely coagulating into acoherent lump, but in thepresence of insuflicient protective to prevent the resin flocs from depositing on the fabric when in contact therewith.

Various methods are known for agglomerating 'or flocculating the dispersed particles of waterinsoluble synthetic resin may be agglomerated by the addition of mildly alkaline salts such sodium carbonate to an aqueous dispersion of the resin in the presence of a protein, such as gelatin,

or in the presence of a cationic soap. The

persing agent for the dispersed resin particles. may also act as the stabilizer or protective during the flocculation to prevent lump coagulation oi the resin- Another method of agglomerating the resin particles is to precipitate a flocculant salt or acid in the dispersion of synthetic resin, as by precipitating a polyvalent metal silicate or silicic acid gelin the protected resin dispersion. A preferred method is by treating the synthetic resin dispersion with a monovalent salt of a strong acid in the presence of both clay and a protein, such as gelatin, and also a protective for the agglomerates.

Various well known protectives or stabilizers may be used to prevent the flocs in the bath from completely coagulating into av coherent mass. The amount of stabilizer necessary to protect the agglomerates will depend on the specific protective used, the method of agglomeration, and the temperature and concentration of the bath, but

, have a straight chain or ring structure, and may contain substituent halogen, amine, nitro or hydroxyl groups, and the M may be an alkali metal, hydrogen or ammonium radical. I have found very satisfactory in the present invention, protectives having the general formula R-SOaM, where R represents an organic radical containing at least one group containing more than 8 carbon atoms and M represents alkali metal, hydrogen or ammonium radical. Various commercial Itabilizers having thls general formula W are illustrated below with reference to various classifications of the radical R:

(1) WhereR is an aikoxy group producing, as for example, various compounds from C1oH2iO SOaNa to CraHarO-SOaNa, known commercially under the trade names Gardinol, Duponol, Aquarex D, Orvus WA.

(2) Where R is analkyl group producing, as for example in the formulae CnHzs-SOsNa and C1cHaa-"BOaNa, lauryl' sodium sulphonate and cetyl sodium sulphonate, respectively.

(3) Where R is a mixedether of long and short chain aliphatic groups, as for example in the compound CriHaa-O-CzHe-SOhNB. believed to be the material known commercially as NacconolLA.

(4) Where R is an alkyl ester. of a long chain fatty alcohol, as for example in the compound cuna-c-o-cinr-soim I g known commercially by the trade-names Igepon A'and Arctic Byntex'A. u

- (5)'-Where Risa glycol, esterof a long chain fatty-alcohol, asforexa'mple in the formula gelatin orcationic soap. which may be the dis 2,s4o,ssa g l (6) Where a is an alkyl substituted amid a.

fatty acid, as for example in the compounds believed to be the commercial products Igepon T and Igepon TF, respectively. I

(7) Where R is an alkyl substituted aromatic radical as in various commercial compounds having the formula lkyi I }40:M

as for example, the sodium salts ofalkyl naphthalene sulphonic acid, known under the trade names Nekal; Alkanol; a free alkyl naphthalene known under the trade name Octaton. Also where R is a hydroaromaticradical as in various commercial compounds having the formula H g Y as for example, where M is sodium as in Alk-anol S and Mayamin; where M is potassium as in Mayaminkalium; and where M is ammonium as in Mayammonium.

(9) Where R is an ester of a dibasic acid, such as Ha I -H R3O.=0 in which one of R1 and Rs may be an alkyl radical fr0m-C3H'ito CaI-Inand the other hydrogen, or both R1 and R: such as alkyl radical, as for example inthe commercial stabilizer known as Aerosol OT which has the formula CsHn-OC=O I n -SOzNa Ct i10 =0 The water-insoluble synthetic resin may be of any type to impart the desired properties to the fabric, for. example, phenol-aldehyde resins, urea aldehyde resins, melamine-aldehyde resins, aro

matic amine-aldehyde resins, synthetic linear organic p lyamids (condensation polymerization of a diamine and a dibasic carboxylic acid e. g. hexamethylene diamine and adipic acid), acrylic resins (polymers or copolymers of the monomeric derivatives, 1. e. esters, amides, salts, halides, or nitriles of acrylic acid or methacrylic acid), alkyd resins (polydric alcohol-polybasic acid polymers), polyterpene resins (polymerization of turpentine or copolymerization of turpentine residue and fish oil), polymerized vinyl esters (including copolymers of different esters), polymerized vinyl acetals, polymerized vinylidene esters, copolymers of vinyl and vinylidene esters, poly. styrene, polyvinyl naphthalene, cellulose esters, ethyl cellulose, sulphurized vegetable oils (factice), polyisobutylene, and the various water insoluble synthetic resins which are the so-called synthetic rubber or rubber-like materials, namely, butadiene polymers (polymerized butadiene- 1,3, chloro-2-butadiene-1,3 (neoprene), methyl-2-butadiene-l,3, 2,3-dimethyl butadiene-1,3), copolymers of a major proportion of a butadiene and a minor proportion of a monovinyl compound copolymerizable therewith such as styrene ("Buna S) or acrylic nitrile (Buna N), copolymers of a major proportion of isobutyleneand a minor proportion of a diolefine copolymerizable therewith such as butadiene-1,3 or 2-methyl butadiene- 1,3 (isoprene), or 2,3-dimethyl butadiene-1,3 or pentadiene-1,3 (Butyl rubbers), organic polysulphide polymer plastics (commercially known as 'I'hiokols and which are substantially polymers of the structural unit .ai s....

or the structural unit where represents two carbon atoms separated by and joined to an intervening structure such as an ether linkage, unsaturated carbon atoms, aromatic structure, saturated straight chain hydrocarbons, or saturated branch chain hydrocarbons as described in the Patrick Patents Nos. 1,890,191 and 2,216,044, respectively).

In carrying out the process of the invention, the. fabric is immersed in a bath of an agglomerated water-insoluble resin composition as described above, until the desired amount of' resin fiocs has deposited on the fabric, after which the if the resin particles have been floccuaddition of an acid salt such as ammoniexample, lated by um sulphate, small amounts of acid maybe added during the deposition, and if the resin particles have been fiocculated by addition of an alkaline salt, such as sodium carbonate, small amounts of alkaline material may be added during the deposition. The treating bath may contain up to 2% water-insoluble synthetic resin and where weight ratio of bath to fabric is not too high, all of the iiocculated resin particles may be deposited. The ratio of treating bath to fabric and the concentration of resin in the bath determine the amount of resin deposit on the fabric. The bath before drying.

Various examples of the treatment of fabrics are set forth below, but these are merely exemplary of the invention and are not intended to be limitations thereof.

Example I In this case rayon stockings were treated with a methacrylate resin. The starting material was a commercial emulsion supplied by E. I. du Pont de Nemours 8: 00., under the trade name "Methacrylate-NH Emulsion," which is an aqeuous dispersion of polymerized methyl methacrylate.

In making up the treating bath from the Methacrylate-NH Emulsion, 16 lbs. of water were placed in a stainless steel container at 110 F. 3 ounces of a 5% aqueous solution of Aquarex D, a stabilizer having the composition mono sodium sulphate ester of one-half lauryl and one-half myristyl alcohol, were added, and then, in order, were added 1 oz. of Methacrylate-NH Emulsion" containing 40% resin, 1 oz. of a 40% aqueous clay dispersion and 5 oz. of 3% aqueous gelatin solution. The bath was well stirred and 3 lbs. of 33 /Zi% aqueous fabric may be rinsed or washed, and dried. The

fabrics may be woven or' knitted and may be made of various kinds of fibers, such as silk, wool, cotton, linen, viscose rayon, acetate rayon, cuprammonium rayon, synthetic fibers such as nylon, and the like, or various combinations of the same. The process of the present invention is particularly adapted to the treatment of knitted fabrics, such as stockings, where the treatment imparts to the stockings an appearance of having been knit from finer yams or on finer gauge machines in addition to enhancing the wearing qualities and reducing the tendency to snag.

The fabric, according to the present invention,

is immersed in a bath where the weight ratio of treating bath to fabric ranges from 10:1 to 80:1, or over, and the fabric is permitted to remain in the bath until the desired amount of flocs is deposited on the fabric. Small amounts of acid or alkali may be added to the bath during the deposition treatment depending on the method used in agglOmerating-the resin particles. For

solution of ammonium sulphate were added. 0n addition of the ammonium sulphate, the dispersed particles in the bath immediately agglomerated and on removing a portion of the bath from the container in a graduate for inspection, the flocs could be seen to settle immediately.

A dozen pairs of all-rayon full-fashioned ladies stockings which weighed one pound, were introduced into a cotton bag and placed into the bath. The stockings were agitated in the bath and after 10 minutes, 1% oz. of 10% formic acid were added, followed by 2 oz. of the 10% formic acid solution after 10 more minutes, and again 2 oz. more after 10 more minutes. At ,the end of 15 more minutes, or 45 minutes total treatment, the stockings in the cotton bag were removed. The bath was clear. The stockings were rinsed in fresh water, removed, the excess water extracted in a centrifuge, and the stockings dried on heated forms in the usual manner. The stockings were found to have gained 3% in weight, the balance of the resin having deposited upon the cotton bag. The hosiery had a very sheer appearance and had improved resistance to bagging, snagging and wear.

Example II In this case stockings were treated with a fiocculated "Nypene Emulsion 1802 supplied by The Neville Company. This was an aqueous dispersion of a polyterpene resin made by the catalytic polymerization of turpentine.

In preparing the treating bath, 92 lbs. of water were introduced into the stainless steel container, followed by 6 oz. of a solution of Aquarex D, 2 oz. of a 40% emulsion of "Nypene Emulsion 1802, 2 oz. of a 40% aqueous clay dispersion, and oz. of a 3% gelatin solution. 6 lbs. of a 33% aqueous solution of ammonium sulphate were added and the material in the bath flocculated immediately.

Two dozen pairs of ladies stockings with rayon legs and cotton plated feet weighing 2 lbs. were introduced into the bath and agitated therein, and after 10 minutes 2 /2 oz. of aqueous 10% formic acid was added, followed by 5 oz. of the formic acid solution after 10 minutes, and 5 oz. again after 10 more minutes. The stockings were removed from the bath after 45 minutes from the time of initial immersion. The bath was clear and the stockings were found to have gained 3.2% in weight. The stockings showed marked improvement in appearance and wearing qualities.

Example III In this case the fabric was treated with polyvinyl acetate resin. The starting material was polyvinyl acetate emulsion RH 460 A supplied by E. I. du Pont de Nemours & Co., which is an aqueous dispersion of polyvinyl acetate resin. The emulsion contained 40% of the resin.

The treating bath was made up by introducing 155 lbs. of water into a stainless steel container and adding thereto 1 lb. of 5% aqueous solution of Aquarex D, 5 oz. of the 40% "RH-460 A polyvinyl acetate resin, 5 oz. of the 40% aqueous clay dispersion, and 1.5 oz. of the 3% gelatin solution. The bath was then fiocculated by adding thereto pounds of a 33%% aqueous solution of ammonium sulphate,

Four dozen pairs of cotton-top rayon stockings weighing 5 lbs. were introduced into the bath in the usual cotton bag, and after 10 minutes of agitating, 6 oz. of 10% aqueous solution of formic acid was added, followed by 12 oz. of the 10% formic acid after 10 more minutes, and then 12 oz. again after a further 10 minutes. The stockings were removed from the bath 45 minutes after initial immersion and the bath was clear. The gain in weight on the stockings was found to be 4%. Marked improvement in appearance and wearing qualities of the stockings was noted.

Example IV In this case stockings were treated with polymerized butyl methacrylate.

The butyl methacrylate polymer dispersion was prepared by plasticizing 100 parts of the commercial polymer with 50 parts of butyl 'benzyl sulphonamide, milling in parts of alkali-solubilized casein as a dispersing agent, and then adding water slowly in a Werner 8: Pfleiderer mixer until an inversion in phase took place and the resin became dispersed in the aqueous medium, and adding further water to a concentration of 50% solids (all parts designated herein are by weight). To the 340 parts of the dispersion of the butyl methacrylate polymer was added 105 parts of a 24-hour ball-milled aqueous clay dispersion containing 50 parts of Dixie clay and 5 parts of "Aquarex D, 1200 parts of a 3% gelatin solution, and 560 parts water.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 20:1. The bath contained 50 parts of the above dispersion of the butyl methacrylate and clay. 150 parts of a 33 solution of ammonium sulphate, and 25 parts of a 10% solution of Aquarex D," per parts of hosiery.

The stockings which were viscose rayon were introduced into the bath at 110 F., and after 5 minutes, 5 parts of 10% aqueous formic acid per g 100 parts of hosiery were added, followed by 10 parts of 10% formic acid after 5 more minutes, and then 10 parts of 10% formic acid after a further 5 minutes. The stockings were removed from the bath after 30 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed twice at 110 F. in 20:1 rinse baths containing 50 parts of 10% formic acid per 100 parts of hosiery, extracted, and dried. The gain in weight on the stockings was 3.3%.

Example V In this case stockings were treated with Vinsol Plastic, which is a copolymer of Vinsol (the still residuum after the distillation of turpentine) and fish oil.

The Vinsol Plastic dispersion was prepared by compounding 100 parts of the commercial Vinsol Plastic with 4 parts of sulphur and 10 parts of zinc oxide, milling in 1 part of alkali-solubilized casein and 8 parts of dimethylamine soap as dispersing agents, and then adding water slowly in a Werner & Pfleiderer mixer until an inversion of phase took place and the plastic became dispersed in the aqueous medium, and adding further water to a concentration of 50% solids. To the 246 parts of the dispersion of the Vinsol Plastic was added parts of a 24-hour ball-milled aqueous clay dispersion containing 50 parts of Dixie clay and 5 parts of Aquarex D, 1200 parts of a 3% gelatin solution, and 100 parts of water.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 20:1. The bath contained 45 parts of the above dispersion of the Vinsol Plastic and clay, 27 parts of a 10% solution of Aquarex D, and 150 parts of 33 solution of ammonium sulphate, per 100 parts of hosiery.

The stockings which were viscose rayon were introduced into the bath at F. and after 10 minutes 5 parts of 10% formic acid per 100 parts of hosiery were added, followed by 10 parts of weight on the stockings was 3.5%.

Example VI In this case viscose rayon stockings were treated with commercial polyvinyl butyral.

The polyvinyl butyral as obtained contained 7 parts of a plasticizer per 100 parts of the polyvinyl butyral resin. The dispersion was prepared by plasticizing 107 parts of the polyvinyl resin The stockings were removed from the as received with 50 parts of castor oil, milling in 15 parts of ammonium soap, and then adding water slowly in a Werner 8: Pfleiderer mixer until an inversion of phase took place and the resin became dispersed in the aqueous medium, and adding further water to a concentration of 55% solids. To the 312 parts of the dispersion of the polyvinyl butyral was added 105 parts of a 24-hour ball-milledaqueous dispersion contain- 1 ing 50 parts of Dixie clay and parts of Aquarex D, and 1200 parts of a 3% gelatin solution.

.A flocculated treating bath was prepared in which the ratio of bath to stockings was 40:1. The bath contained 38 parts of the above polyvinyl butyral and clay dispersion, 300 parts of a 33 solution of ammonium sulphate, and 25 parts of a solution of Aquarex D, and 1 part of a 10% formic acid solution, per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F. and after minutes and again after 15 more minutes, 1.5 parts of 10% formic acid per 100 parts of hosiery were added. The stockings were removed from the bath after 45 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed twice in 40:1

aqueous medium, and adding further water to a concentration of 10%. I

A- flocculated treating bath was prepared in which the ratio of bath to stockings was 35:1. The bath contained 55 parts of the above ethyl cellulose dispersion, parts of a 10% solution of the protective "Igepon T, 250 parts of a 33 solution of ammonium sulphate, and 1 part of a 10% formic acid solution, per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F. and after 15 minutes and again after 15 more minutes 1.5 parts of 10% formic acid per 100 parts of hosiery were added. The stockings were removed from the bath after 45 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed twice in 1 35:1 rinse baths containing 2 parts of 10% formic rinse baths containing 1 part of 10% formic acid per 100 parts of hosiery, extracted, and

dried. The gain in weight on the stockings was Example VII In this case viscose rayon stockings were treated with a flocculateddispersion of a phenolformaldehyde resin. The starting material was a commercial aqueous phenol-formaldehyde dispersi0n-Durez Emulsion No. 2-9230, supplied by the Durez Plastics & Chemical Inc. The dispersion contained 50% solids.

To 100 parts of the dispersion of the phenolformaldehyde resin was added 105 parts of a 24- hour ball-milled dispersion containing 50 parts of Dixie clay, and 5 parts of Aquarex D.

A flocculated treating bath was prepared in which the ratio of bath to stockings :to be treated was 40:1. The bath contained 12 parts of the above phenol-formaldehyde and claydispersion, 150 parts of a 33%% solution of ammonium sulphate, 25 parts of a 10% solution of Aquarex D, and 1 part of a 10% formic acid solution, per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F. and after 15 minutes and again after 15 more minutes 1.5 parts of 10% formic acid solution per 100 parts of hosiery were added. The stockings were removed from the bath after 45 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed twice in 40:1 rinse baths containing 1 part of a 10% formic acid solution per 100 parts of hosiery, extracted, and dried. The gain in wei ht on the stockings was 3.4%. 1

Example VIII In this case cuprammonium rayon stockings.

. 25 parts of dibutyl phthalate, milling in 8 parts of diethylamine soap as a dispersing agent, and then adding water slowly in a Werner.& Pileiderer mixer until an inversion in phase took place and the Ethocel became dispersed in the acid per parts of hosiery, extracted, and dried. The gain in weight on the stockings was 3.2%.

Example IX In this case viscose stockings were treated with commercial polyisobutylene furnished by Standard Oil Company of New Jersey under the trade name Vistanex.

The dispersion of polyisobutylene was prepared by milling in 20 parts of alkali solubilized casein and 2 parts of diethylamine soap per 100 parts of polyisobutylene as dispersing agents, and then adding water slowly in a Werner & Pfieiderer mixer until an inversion of phase took place and the resin became dispersed in the aqueous medium, and adding further water to a concentration of 50% solids.

To 244 parts of the isobutylene dispersion was added parts of a 24-hour ball-milled dispersion containing 50 parts of Dixie clay and 5 parts of Aquarex D," 1200 parts of a 3% gelatine solution, and 100 parts of water.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 20:1. The bath contained 45 parts of the above polyisobutylene and clay dispersion, 12 parts of a 10% solution of Aquarex D and 150 parts of a 33 solution of ammonium sulphate, per 100 parts of hosiery.

The stockings were introduced into the bath at F. and after 10 minutes 1 part of 10% aqueous formic acid per 100 parts of hosiery was added, followed by 2 parts of 10% of formic acid after 5 more minutes, and then 2 parts of 10 7/ formic acid after a further 5 minutes. The stockings were removed from the bath after 40 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed once at Example X In this case viscose rayon stockings were treated with a polyhydric alcohol-polybasic acid polymerNoropol made by the condensation polymerization of so-calledsoybean acid and ethylene glycol.

100 parts of the- Noropol were first compounded with 25 parts ester gum, 50 parts zinc oxide, 5 parts sulphur and 2 parts mercaptobenzothiazole, (accelerator), and the compound cured or vulcanized by heating for 3 hoursat C. The 182 parts of the cured Noropol'were dispersed in a Werner 8: Pfleiderer mixer on 36 -monia after a further minutes.

parts of gelatin with addition of water to a 50% solids dispersion in the conventional manner.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 20:1. The'bath contained 10 parts of the 50% solids dispersion of the Noropol, 25 parts of 10% solution of-Aquarex D," 150 parts of a 33 70 solution of ammonium sulphate, and 1 part of 10% formic acid solution, per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F. and after minutes and again after 15 more minutes 1.5 parts of 10% formic acid per 100 parts of hosiery were added. The stockings were removed from the bath after 45 minutes. The bath which was clearwas discarded. The stockings were rinsed twice in a :1 rinse bath containing 2 parts of 10% formic acid per 100 parts of hosiery, extracted, and dried. The

gain in weight on the stockings was 8.2%.

Example XI In this case viscose rayon stockings were treated with a flocculated dispersion of Noropol dispersed on gelatin which also acted as the protective to prevent lump coagulation of the dispersion on flocculation.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 20:1.

- The Noropol dispersion used was the same 50% solids dispersion as in Example X in which 182 part-s of the cured Noropol was dispersed on 36 parts of gelatin. The bath contained 6 parts of the 50% Noropol dispersion per 100 parts of hosiery and 3 /2 parts of a 24-hour ball-milled 40% dispersion of Dixie clay containing .8% gelatin. The bath was flocculated by the addition of 10 parts of a 5% aqueous solution of sodium carbonate, per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F. and after 5 minutes 1 part of 10% aqueous ammonia per 100 parts of hosiery was added, followed-by 2 parts of 10% ammonia after 5 more minutes-and then 2' parts of 10% am- The stockings were removed from the bath after 20 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed once at 110 F. for 5 minutes in a 20:1 rinse bath containing 5 parts of 10% ammonia per 100 parts of hosiery, extracted, and dried. The gain in weight on the stockings was 2.7%.

Example XII In this case viscose rayon stockings were treatedwith a, Noropol dispersion dispersed on a cationic soap which also acted as the protective to prevent lump coagulation of the dispersion on flocculation.

A fiocculated treating bath was prepared in which the ratio of bath to stockings was 20:1. 100 parts of the Noropol were first com unded with 25 parts of ester gum, 50 parts zinc oxide, 5 parts sulphur and 2 parts mercaptobenzothiazole (accelerator), and the compound cured or vulcanized by heating for 3 hours at 150 C. The 182 parts of the cured Noropol were dispersed in 3. Werner & Pfleiderer mixer by mixing in 36 parts of a cationic base, mu-heptadecyl-N-hydroxyethyl imidazoline, and 6 /2 parts of glacial acetic acid to saponify the cationic base in situ and form the cationic soap, followed by the grad- The bath contained 6 /2 parts of the 50% Nowpol dispersion per parts of hosiery, and 3% parts of a 24-hour ball-milled 40% dispersion of Dixie clay containing .7% of acetic acid saponified mu-heptadecyl-N-hydroxyethyl imidazoline. The bath was flocculated by the addition of 10 parts of a 5% aqueous solution of sodium carbonate per 100 parts of hosiery.

The stockings were introduced into the bath at F. and after 5 minutes 1 part of 10% aqueous ammonia per 100 parts of hosiery was added, followed by another 1 part of 10% ammonia after 5 more minutes, and then 1 part of 10% ammonia after a further 5 minutes. The stockings were removed from the bath after 20 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed once at 110 F. for 5 minutes in a 20:1 rinse bath containing 2' parts of 10% ammonia per 100 parts of hosiery, extracted,

and dried. The gain in weight on the stockings was 4.2%.

Example XIII 40% solids content supplied by Stamford Rubber Supply Company.

A flocculated treating bath was prepared in which the ratio of stockings to ,bath was 30:1. The bath contained 15 parts of the factice dispersion, 25 parts of a 10% solution of a commercial liquid stabilizer of unknown composition, sold by E. I. du Pont de Nemours & Co. under the trade name MP-189-S Crude, and which as stated by them to be a sulphonated petroleum product made to replace Aquarex D, 250 parts of 33%% solution of ammonium sulphate, and 1 part of a 10% solution of formic acid per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F., after 15 minutes and again after 15 more minutes 1.5 parts of 10% formic acid per 100 parts of hosiery were added. The stockings were removed from the bath after 45 minutes. The bath was discarded, and the stockings were rinsed twice in 35:1 rinse baths containing 2 parts of 10% formic acid per 100 parts of hosiery, extracted, and dried. The gain in weight on the stockings was 2.4%.

Example XIV In this case viscose rayon stockings were treated with a butadiene polymer, namely polymerized chloro-2-butadiene-1,3, known as neoprene. The starting material was Neoprene No. 571 Latex which is a 50% dispersion of polychloroprene supplied by E. I. du Pont de Nemour 8: Co.

To 200 parts of the neoprene dispersion was added parts of a 10% solution of Aquarex D, 1200 parts of a 3% solution of gelatin, and 105 parts of a 24-hour ball-milled aqueous dispersion containing 50 parts of Dixie clay and 5 parts of Aquarex D, and 280 parts of water.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 20:1. The bath contained 50 parts of the above dispersion of neoprene and clay, 35 parts of a 10% solution of Aquarex D, and parts of 33 solution of ammonium sulphate, per 100 parts of hosiery.

The stockings were introduced into the bath at 110 F. and after 5 minutes 1 part of a 10% formic acid per 100 parts of hosiery was added, followed by 2 parts of a 10% aqueous formic acid after 5 more minutes, and-then 2 parts of 3.5 parts of formic acid per 100 parts of hosiery, extracted, and dried. The gain in weight v on the stockings was 2.5%.

Example XV In this case stockings were treated with a copolymer of butadiene and styrene, known as.

Buna S. The starting material was the product of the emulsion-copolymerization of 75 parts butadiene-1,3 and parts by weight of styrene in the presence of suitable protectives. To the dispersion was added suitable vulcanizing ingredients. The prepared curing dispersion was a 36% solids content dispersion.

To 305 parts of the 36% Buna S dispersion was added 800 parts of a 3% gelatin solution, and 240 parts of water.

A flocculated treating bath was prepared in which the ratio of bath to stockings was 18:1. The bath contained 50 parts of the diluted Buna S dispersion containing the gelatin, 25 parts of a 10% solution of Aquarex D, and 120 parts of a /596 solution of ammonium sulphate, per 100 parts of hosiery.

The stockings which were viscose rayon were introduced into the bath at 110 F. and after 10 minutes 1 part of 10% aqueous formic acid was added per 100 parts of hosiery, followed by 2 parts of 10% formic acid after another 10 minutes, and then 2 parts of 10% formic acid after 10 more minutes. The stockings were removed from the bath after 40 minutes. The bath which was slightly hazy was discarded. The stockings were rinsed once at 110 F. in an 18:1 rinse bath containing 5 parts of 10% formic acid per 100 parts of hosiery, extracted, and dried. The gain in weight on the stockings was 2%.

This is a continuation-in-part of application Serial No. 428,050, filed January 24, 1942.

In view of the many changes and modifications that maybe made without departing from the principles underlying the invention, reference should be made to the appended claims for an understanding of the scope of the protection afforded the invention.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin in which the resin agglomerates are macroscopic and readily separable from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10: 1 and 80:1 and said bath being capable of depositing its resin agglomerates on said fabric on contact therewith, and maintaining said fabric associated with said bath until the desired amount of flocculated resin particles has depossited on the fabric.

2. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated dispersion of water-insoluble synthetic resin in which the resin agglomerates are in the form of composite particles comprising water-insoluble synthetic resin and clay which are macroscopic and readily separable as such composite particles from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10:1 and 80:1 and said bath I r l.)

being capable of depositing its resin agglomerates on said fabric on contact therewith, and maintaining said fabric associated with said bath until the desired amount Of composite particles has deposited on the fabric.

3. The process of treating fabrics which comprises. immersing afabric in an aqueous bath of an agglomerated aqueous dispersion of waterinsoluble synthetic resin in which the resin 21%- glomerates are macroscopic and readily separable from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10:1 and 80:1 and said bath containing sufficient protective to prevent the resin agglomerates from completely coagulating into a co herent lump but insufiicient protective to prevent the agglomerates from depositing on the fabric, and maintaining said fabric associated with said bath until the desired amount, of fiocculated resin particles has deposited on the fabric.

4. The process of treating fabrics which com-. prises immersing a fabric-in an aqueous bath of i an agglomerated dispersion of water-insoluble synthetic resin in which the resin agglomerates are in the form of composite particles comprising water-insoluble synthetic resin and clay which are macroscopic and readily separable as such composite particles from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10:1 and 80:1 and said bath containing suflicient protective to prevent the resin agglomerates from completely coagulating into a coherent lump but insufflcient protective to prevent the agglomerates from depositing on the fabric, and maintaining said fabric associated with said bath until the desired amount of composite particles has deposited on the fabric.

5. .The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin in which the resin agglomcrates are macroscopic, said bath being capable of depositing its resin aggregates on said fabric on contact therewith, and maintaining said fabric associated with said bath until the desired amount of flocculated resin particles has deposited on the fabric.

6. The process of treating fabrics'which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin in which the resin agglomerates are macroscopic, said bath containing sufllcient protective to prevent the resin agglomerates from completely coagulating into a coherent lump but insuflicient protective to prevent the agglomerates from depositing on the fabric, and maintaining said fabric associated with said bath until the desired amount of fiocculated resin particles has deposited on said fabric.

'7. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin containing up to 2% water-insoluble synthetic resin and in which the resin particles are macroscopic and readily separable from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10:1 and :1, and said bath being capable of depositing its resin agglomerates on said fabric on contact therewith, and maintaining said fabric associated with said bath until the desired amount of flocculated resin particles has deposited on the fabric.

8. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated dispersion of water-insoluble synthetic resin containing up to 2% water-insoluble synthetic resin and in which the resin agglomerates are in the form of composite particles comprising water-insoluble synthetic resin andclay which are macroscopic and readily separable as such composite particles from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10:1 and 80:1 and said bath being capable M depositing. its resin agglomerates on said fabric on contact therewith, and maintaining said fabric associated with said bath until the desired amount of composite particles has deposited on the fabric.

9. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin containing up to 2% water-insoluble synthetic resin and in which the resin agglomerates are macroscopic and readily separable from the aqueous medium on standing, the weight ratio of said bath to said fabric being between 10:1 and 80:1 and said bath containing suflicient protective to prevent the resin agglomerates from completely coagulating into a coherent lump :but insufficient protective to prevent the agglomerates from depositing on the fabric, and maintaining said fabric associated with said bath until the desired amount of flocculated resin particles has deposited on the fabric.

10. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated dispersion of water-insoluble synthetic resin containing up to 2% water-insoluble synthetic resin and in which the resin agglomerates are in the form of composite particles comprising water-insoluble synthetic resin protective to prevent the agglomerates from depositing on the fabric, and maintaining said fabric associatedrwith said bath until the desired amount of composite particles has deposited on the fabric. I

11. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin containing up to 2% water-insolu-ble synthetic resin and in which the resin agglomerates are macroscopic, said :bath being capable of depositing its resin aggregates on said fabric on contact therewith, and maintaining said fabric. associated with said bath until the desired amount of flocculated resin particles has deposited on the fabric.

12. The process of treating fabrics which comprises immersing a fabric in an aqueous bath of an agglomerated aqueous dispersion of water-insoluble synthetic resin containing up to 2% water-insoluble synthetic resin and in which the resin agglomerates are macroscopic, said bath containing suflicient protective to prevent the resin agglomerates from completely coagulating into a coherent lump but insuflicient protective to prevent the agglomerates from depositing on 

